US4618435A - Organic titanium compositions for use in oil and gas wells - Google Patents

Organic titanium compositions for use in oil and gas wells Download PDF

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US4618435A
US4618435A US06/823,122 US82312286A US4618435A US 4618435 A US4618435 A US 4618435A US 82312286 A US82312286 A US 82312286A US 4618435 A US4618435 A US 4618435A
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amino alcohol
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Donald E. Putzig
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/66Compositions based on water or polar solvents
    • C09K8/68Compositions based on water or polar solvents containing organic compounds
    • C09K8/685Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00Earth boring, well treating, and oil field chemistry
    • Y10S507/903Crosslinked resin or polymer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00Earth boring, well treating, and oil field chemistry
    • Y10S507/922Fracture fluid

Definitions

  • the present invention relates to dry, solid compositions containing an organic titanate/amino alcohol reaction product plus a mono- or disaccharide or a polyhydric alcohol derivable from a monosaccharide.
  • the compositions are useful in preparing thixotropic cements and fluid fracture formulations for use in oil and gas wells.
  • titanium esters react with high molecular weight hydroxyl-containing compounds so as to crosslink them and produce gels; J. Oil and Colour Chem. Assoc. 31, 405 (1948).
  • the crosslinking reaction made through the use of simple alkyl esters of titanium proceeds too rapidly for most industrial uses.
  • the crosslinking rate imparted by titanium esters can be depressed by combining a titanium ester with a variety of multifunctional compounds, including triethanolamine.
  • the reaction product of tetraisopropyl titanate (also known as tetraisopropoxytitanium) and triethanolamine, at a titanate:triethanolamine mol ratio of 1:2 finds several industrial uses. Among others, that reaction product is used to crosslink high molecular weight compounds (e.g., hydroxypropyl guar gum), and the crosslinked high molecular weight material is used to fracture oil-bearing formations; that type of use is disclosed in U.S. Pat. No. 3,888,312.
  • the reaction product of tetraisopropyl titanate and triethanolamine, at a titanate:triethanolamine mol ratio of 1:1 has had little if any industrial use. On the other hand, it has been disclosed in U.S. Pat. No. 2,950,174.
  • thixotropic cements in oil and gas wells is well known; see for example U.S. Pat. Nos. 2,890,752 and 3,804,174.
  • Portland cement is combined with a hydrocarbon liquid and an alkali metal soap.
  • a hydraulic cement (such as Portland, aluminous or pozzolanic hydraulic cement) is combined with a cellulose ether and a salt of zirconium, lead, chromium, ferric iron, hafnium, lanthanum or yttrium, preferably zirconium oxychloride.
  • compositions of the present invention provide a number of advantages over those disclosed heretofore.
  • zirconium oxychloride is more toxic than the titanium compounds; it adversely affects the set rate of the cement and does not effect thixotropy in cements over the broad range of temperatures normally encountered in most wells, viz. 60°-135° C.
  • the reaction product of tetraisopropyl titanate and triethanolamine at a titanate:triethanolamine molar ratio of 1:2 did not perform satisfactorily in cements at the lower temperatures, and it is a liquid whereas a solid is preferred for dry blending with cement. If one attempts to remove water and/or alcohol from the products of U.S. Pat. Nos.
  • composition of the present invention comprises a dry, solid mixture of
  • titanate:amino alcohol mol ratio in the range between about 1:1 and about 2:1
  • an additive in an amount sufficient to enhance the uniform crosslinking capacity of said reaction product, which additive is a monosaccharide, a disaccharide, or a polyhydric alcohol which can be obtained by reduction of a monosaccharide,
  • R 1 is alkyl containing 1-6 carbon atoms
  • each of R 2 , R 3 and R 4 is alkylene containing 1-6 carbon atoms
  • R 5 is H or alkyl containing 1-6 carbon atoms
  • k is 1-3 and g plus k equals 3;
  • n 1 or 2 and m plus n equals 2.
  • tetraisopropyl titanate is the titanate of choice.
  • Triethanolamine, triisopropanolamine, tetrakis(hydroxyisopropylethylenediamine) and tetrakis(hydroxyethylethylenediamine) are examples of amino alcohols which are useful in the invention, with triethanolamine being preferred.
  • Glucose, fructose, mannose, galactose and xylose are examples of monosaccharides useful in the invention, with glucose and fructose being preferred, particularly the latter.
  • Sucrose, lactose, maltose and cellobiose are examples of disaccharides useful in the invention, with sucrose being preferred.
  • Erythritol, arabitol, xylitol, sorbitol, dulcitol and mannitol are examples of polyhydric alcohols which can be obtained by reduction of a monosaccharide and which are useful according to the invention.
  • Sorbitol is the preferred polyhydric alcohol for the purposes of the invention.
  • the proportion of the monosaccharide, disaccharide or polyhydric alcohol which is added to the titanate/amino alcohol reaction product varies over a wide range. It depends on a variety of factors: whether the composition is to be used in a thixotropic cement or in a fluid fracture formulation and the conditions encountered in either such use, the well depth, the types of strata encountered in the well, the identity of the titanate/amino alcohol reaction product, the identity of the additive (monosaccharide, disaccharide or polyhydric alcohol), and the like.
  • the additive:reaction product weight ratio is in the range between 1:10 and 10:1. Preferably, that ratio is in the range between about 3:10 and about 1:1. In the case of fructose, most preferably the weight ratio of fructose to the reaction product is in the range between 3.5:10 and 4:10.
  • the titanate/amino alcohol reaction product can be prepared by reacting equimolar proportions of the titanate and the amino alcohol and isolating the reaction product as a dry solid by removal of the isopropanol liberated in the reaction.
  • the reaction can be run at ambient temperature or at elevated temperature.
  • the amino alcohol can be added with agitation to the titanate over a period of about one hour at a temperature in the range between about 40° and 50° C. Thereafter, agitation is continued in that temperature range for about 4 hours. If run at ambient temperature, the 4-hour period should be increased to about 8 hours.
  • a variety of techniques may be used to remove the isopropanol liberated in the reaction. For example, a rotary vacuum ribbon dryer can be used, as can a graining bowl under vacuum. After separation of the reaction product from the isopropanol liberated in the reaction, it is dry blended with the additive.
  • Triethanolamine was added to tetraisopropyl titanate in a 1:1 mol ratio with agitation at 45°-50° C. over a period of one hour. Thereafter the reaction mixture was agitated for an additional period of about 4 hours at the same temperature.
  • the reaction resulted in the liberation of isopropanol at an isopropanol:titanium mol ratio of about 3:1, giving a reaction product weighing 433 g.
  • the isopropanol was evaporated from the reaction product in a rotary dryer over a period of about 2 hours at about 50° C. and about 30 inches of mercury vacuum to give 253 g of a dry solid product. The foregoing procedure was repeated so as to provide materials necessary to run the tests described below.
  • Example 1 The reaction of Example 1 was repeated with triisopropanolamine at a tetraisopropyl titanate:triisopropanolamine mol ratio of 1:1 to give 296 g of a dry solid product.
  • Example 1 The reaction of Example 1 was repeated with tetraisopropyl titanate and tetrakis(hydroxyisopropylethylenediamine) at a mol ratio of 1:1 to produce 346 g of a dry solid product.
  • the method for taking viscosity measurements involves the use of the FANN 39 viscometer.
  • the R-1, B-1 bob configuration was used at 80° F. (26.7° C.), 100 rpm (170 sec -1 ) of shear, and the viscosity was noted at various time intervals set forth in the Table.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

A dry, solid mixture of
(a) the reaction product of
(R.sup.1 O).sub.4 Ti
with (i)
H.sub.g N(R.sup.2 OH).sub.k
at a titanate:amino alcohol mol ratio of about 1:1, or (ii)
R.sup.3 [N(R.sup.4 OH).sub.m R.sub.n.sup.5 ].sub.2
at a titanate:amino alcohol mol ratio in the range between about 1:1 and about 2:1, and
(b) a monosaccharide, disaccharide, or polyhydric alcohol which can be obtained by reduction of a monosaccharide, in an amount sufficient to enhance the uniform crosslinking capacity of said reaction product,
wherein
R1 is C1-6 alkyl;
each of R2, R3 and R4 is C1-6 alkylene;
R5 is H or C1-6 alkyl;
k is 1-3 and g plus k equals 3; and
m is 1 or 2 and m plus n equals 2.
Mixtures are useful in thixotropic cements and in fluid fracture formulations for oil wells.

Description

This application is a continuation of application Ser. No. 540,721 filed Oct. 11, 1983, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to dry, solid compositions containing an organic titanate/amino alcohol reaction product plus a mono- or disaccharide or a polyhydric alcohol derivable from a monosaccharide. The compositions are useful in preparing thixotropic cements and fluid fracture formulations for use in oil and gas wells.
It has long been known that titanium esters react with high molecular weight hydroxyl-containing compounds so as to crosslink them and produce gels; J. Oil and Colour Chem. Assoc. 31, 405 (1948). However, the crosslinking reaction made through the use of simple alkyl esters of titanium proceeds too rapidly for most industrial uses. The crosslinking rate imparted by titanium esters can be depressed by combining a titanium ester with a variety of multifunctional compounds, including triethanolamine.
The reaction product of tetraisopropyl titanate (also known as tetraisopropoxytitanium) and triethanolamine, at a titanate:triethanolamine mol ratio of 1:2, finds several industrial uses. Among others, that reaction product is used to crosslink high molecular weight compounds (e.g., hydroxypropyl guar gum), and the crosslinked high molecular weight material is used to fracture oil-bearing formations; that type of use is disclosed in U.S. Pat. No. 3,888,312. The reaction product of tetraisopropyl titanate and triethanolamine, at a titanate:triethanolamine mol ratio of 1:1, has had little if any industrial use. On the other hand, it has been disclosed in U.S. Pat. No. 2,950,174.
In the preparation of both of the foregoing titanate:triethanolamine reaction products, 2-3 mols of isopropanol are liberated from the titanate and it is common to use or sell the reaction product without removing the isopropanol. On the other hand, it has been proposed to react the amino alcohol with the titanate, add a polyhydroxyorganic compound as a stabilizer, evaporate the alcohol liberated in the reaction between the titanate and the amino alcohol, and replace the evaporated alcohol with enough water to dissolve the stabilized amino alcohol:titanate reaction product; see U.S. Pat. No. 2,894,966.
The use of thixotropic cements in oil and gas wells is well known; see for example U.S. Pat. Nos. 2,890,752 and 3,804,174. In the former, Portland cement is combined with a hydrocarbon liquid and an alkali metal soap. In the latter, a hydraulic cement (such as Portland, aluminous or pozzolanic hydraulic cement) is combined with a cellulose ether and a salt of zirconium, lead, chromium, ferric iron, hafnium, lanthanum or yttrium, preferably zirconium oxychloride.
The compositions of the present invention provide a number of advantages over those disclosed heretofore. For example, zirconium oxychloride is more toxic than the titanium compounds; it adversely affects the set rate of the cement and does not effect thixotropy in cements over the broad range of temperatures normally encountered in most wells, viz. 60°-135° C. Similarly, the reaction product of tetraisopropyl titanate and triethanolamine at a titanate:triethanolamine molar ratio of 1:2 did not perform satisfactorily in cements at the lower temperatures, and it is a liquid whereas a solid is preferred for dry blending with cement. If one attempts to remove water and/or alcohol from the products of U.S. Pat. Nos. 2,894,966 and 2,950,174, gummy solids, e.g., having the consistency of molasses, are obtained. Moreover, the liquid products of those patents (e.g., Example VIII of the former and XXIII of the latter) do not effect thixotropy at 60° C. as well as do the products of the invention.
DETAILED DESCRIPTION OF THE INVENTION
In particular, the composition of the present invention comprises a dry, solid mixture of
(a) the reaction product of a titanate represented by the formula
(R.sup.1 O).sub.4 Ti
with (i) an amino alcohol represented by the formula
H.sub.g N(R.sup.2 OH).sub.k
at a titanate:amino alcohol mol ratio of about 1:1, or (ii) an amino alcohol represented by the formula
R.sup.3 [N(R.sup.4 OH).sub.m R.sub.n.sup.5 ].sub.2
at a titanate:amino alcohol mol ratio in the range between about 1:1 and about 2:1, and
(b) an additive, in an amount sufficient to enhance the uniform crosslinking capacity of said reaction product, which additive is a monosaccharide, a disaccharide, or a polyhydric alcohol which can be obtained by reduction of a monosaccharide,
wherein
R1 is alkyl containing 1-6 carbon atoms;
each of R2, R3 and R4 is alkylene containing 1-6 carbon atoms;
R5 is H or alkyl containing 1-6 carbon atoms;
k is 1-3 and g plus k equals 3; and
m is 1 or 2 and m plus n equals 2.
Because it is readily available, tetraisopropyl titanate is the titanate of choice. Triethanolamine, triisopropanolamine, tetrakis(hydroxyisopropylethylenediamine) and tetrakis(hydroxyethylethylenediamine) are examples of amino alcohols which are useful in the invention, with triethanolamine being preferred. Glucose, fructose, mannose, galactose and xylose are examples of monosaccharides useful in the invention, with glucose and fructose being preferred, particularly the latter. Sucrose, lactose, maltose and cellobiose are examples of disaccharides useful in the invention, with sucrose being preferred. Erythritol, arabitol, xylitol, sorbitol, dulcitol and mannitol are examples of polyhydric alcohols which can be obtained by reduction of a monosaccharide and which are useful according to the invention. Sorbitol is the preferred polyhydric alcohol for the purposes of the invention.
The proportion of the monosaccharide, disaccharide or polyhydric alcohol which is added to the titanate/amino alcohol reaction product varies over a wide range. It depends on a variety of factors: whether the composition is to be used in a thixotropic cement or in a fluid fracture formulation and the conditions encountered in either such use, the well depth, the types of strata encountered in the well, the identity of the titanate/amino alcohol reaction product, the identity of the additive (monosaccharide, disaccharide or polyhydric alcohol), and the like. Usually the additive:reaction product weight ratio is in the range between 1:10 and 10:1. Preferably, that ratio is in the range between about 3:10 and about 1:1. In the case of fructose, most preferably the weight ratio of fructose to the reaction product is in the range between 3.5:10 and 4:10.
The titanate/amino alcohol reaction product can be prepared by reacting equimolar proportions of the titanate and the amino alcohol and isolating the reaction product as a dry solid by removal of the isopropanol liberated in the reaction. The reaction can be run at ambient temperature or at elevated temperature. For example, the amino alcohol can be added with agitation to the titanate over a period of about one hour at a temperature in the range between about 40° and 50° C. Thereafter, agitation is continued in that temperature range for about 4 hours. If run at ambient temperature, the 4-hour period should be increased to about 8 hours. A variety of techniques may be used to remove the isopropanol liberated in the reaction. For example, a rotary vacuum ribbon dryer can be used, as can a graining bowl under vacuum. After separation of the reaction product from the isopropanol liberated in the reaction, it is dry blended with the additive.
The following Examples are given in further illustration of the invention but not by way of limitation.
EXAMPLE 1
Triethanolamine was added to tetraisopropyl titanate in a 1:1 mol ratio with agitation at 45°-50° C. over a period of one hour. Thereafter the reaction mixture was agitated for an additional period of about 4 hours at the same temperature. The reaction resulted in the liberation of isopropanol at an isopropanol:titanium mol ratio of about 3:1, giving a reaction product weighing 433 g. The isopropanol was evaporated from the reaction product in a rotary dryer over a period of about 2 hours at about 50° C. and about 30 inches of mercury vacuum to give 253 g of a dry solid product. The foregoing procedure was repeated so as to provide materials necessary to run the tests described below.
EXAMPLE 2
The reaction of Example 1 was repeated with triisopropanolamine at a tetraisopropyl titanate:triisopropanolamine mol ratio of 1:1 to give 296 g of a dry solid product.
EXAMPLE 3
The reaction of Example 1 was repeated with tetraisopropyl titanate and tetrakis(hydroxyisopropylethylenediamine) at a mol ratio of 1:1 to produce 346 g of a dry solid product.
EXAMPLE 4
Portions of the product of Example 1 were blended as follows:
(a) 25 g of fructose plus 67 g of the product of Example 1
(b) 50 g of fructose plus 67 g of the product of Example 1
(c) 25 g of sorbitol plus 67 g of the product of Example 1
(d) 50 g of sorbitol plus 67 g of the product of Example 1
(e) 25 g of glucose plus 67 g of the product of Example 1
(f) 50 g of glucose plus 67 g of the product of Example 1.
The following tests were run on the compositions of Examples 1-4 so as to develop information as to their suitability for use in thixotropic cement and in fluid fracturing. One of the tests measures the rate of crosslinking as a function of time and the other measures viscosity. Both types of tests involve the use of a base gel which was prepared by combining 4.5 g of hydroxypropyl guar with 750 ml of a 2% by weight KCl solution in water. The pH of the base gel was buffered to about pH 7 with fumaric acid and sodium bicarbonate.
In the test for determining the rate of crosslinking, 250 ml of the base gel were introduced into a 400 ml beaker equipped with a paddle blade agitator. The base gel was agitated at about 1250 rpm to develop a vortex in the center of the surface of the base gel in the beaker. An amount of the composition of the invention sufficient to provide 0.00021 mol of titanium was introduced and the time of introduction was noted. The presence of the composition in the gel caused the vortex to close (or disappear). When that occurred, the time was again noted. The period of time it took for the vortex to disappear is set forth as T1 in the Table.
The method for taking viscosity measurements involves the use of the FANN 39 viscometer. The R-1, B-1 bob configuration was used at 80° F. (26.7° C.), 100 rpm (170 sec-1) of shear, and the viscosity was noted at various time intervals set forth in the Table.
__________________________________________________________________________
Rate of                                                                   
Cross-Linking                                                             
            Viscosity (centipoises)                                       
Example                                                                   
     T.sub.1 (seconds)                                                    
            0 Minutes                                                     
                  30 Minutes                                              
                        60 Minutes                                        
                              90 Minutes                                  
                                    Maximum                               
__________________________________________________________________________
1    68.7   8.75  3.65  2.5   1.9   8.75                                  
2    >180*  2.1   0.5   0.4   --    2.1                                   
3    95.0   2.1   4.3   3.0   2.3   10.5                                  
                                       (2 min.)                           
4(a) 5.67   20.3  8.5   6.8   5.6   20.3                                  
4(b) 3.33   11.0  4.9   3.4   2.6   11.0                                  
4(c) 7.28   7.2   4.8   3.7   2.9   8.4                                   
                                       (2.5 min.)                         
4(d) 4.61   5.0   3.75  3.25   2.85 5.8                                   
                                       (2 min.)                           
4(e) 8.05   8.0   2.3   1.4   1.2   8.0                                   
4(f) 4.52   8.0   2.85  1.7   --    8.0                                   
__________________________________________________________________________
 *Test was not run for longer than 180 seconds.                           

Claims (11)

I claim:
1. A composition comprising a dry, water soluble, solid mixture of
(a) the reaction product of a titanate represented by the formula
(R.sup.1 O).sub.4 Ti
with (i) an amino alcohol represented by the formula
H.sub.g N(R.sup.2 OH).sub.k
at a titanate:amino alcohol mol ratio of about 1:1, or (ii) an amino alcohol represented by the formula
R.sup.3 [N(R.sup.4 OH).sub.m R.sub.n.sup.5 ].sub.2
at a titanate:amino alcohol mol ratio in the range between about 1:1 and about 2:1, and
(b) an additive, in an amount sufficient to enhance the uniform crosslinking capacity of said reaction product, which additive is a monosaccharide, a disaccharide, or a polyhydric alcohol which can be obtained by reduction of a monosaccharide,
wherein
R1 is alkyl containing 1-6 carbon atoms;
each of R2, R3 and R4 is alkylene containing 1-6 carbon atoms;
R5 is H or alkyl containing 1-6 carbon atoms;
k is 1-3 and g plus k equals 3; and
m is 1 or 2 and m plus n equals 2.
2. The composition of claim 1 wherein said titanate is tetraisopropyl titanate.
3. The composition of claim 1 wherein said amino alcohol is triethanolamine.
4. The composition of claim 1 wherein said amino alcohol is tetrakis(hydroxyisopropylethylenediamine).
5. The composition of claim 1 wherein said amino alcohol is tetrakis(hydroxyethylethylenediamine).
6. The composition of claim 1 wherein said additive is fructose.
7. The composition of claim 1 wherein said additive is sorbitol.
8. The composition of claim 1 wherein said additive is glucose.
9. The composition of claim 1, 2, 3, 4, 5, 6, 7 or 8 wherein said additive is present in an additive:reaction product weight ratio in the range between about 1:10 and 10:1.
10. The composition of claim 9 wherein said ratio is in the range between about 3:10 and about 1.1.
11. The composition of claim 2 wherein said amino alcohol is triethanolamine, and said additive is fructose which is present in a fructose:reaction product weight ratio in the range between about 3.5:10 and about 4:10.
US06/823,122 1983-10-11 1986-01-27 Organic titanium compositions for use in oil and gas wells Expired - Lifetime US4618435A (en)

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US2950174A (en) * 1956-04-05 1960-08-23 Lagally Paul Preparation and stabilization of water soluble reactive titanium derivatives
US3804174A (en) * 1973-07-20 1974-04-16 Halliburton Co Well cementing method using thixotropic
US3888312A (en) * 1974-04-29 1975-06-10 Halliburton Co Method and compositions for fracturing well formations
US3894966A (en) * 1973-10-19 1975-07-15 Universal Oil Prod Co Method of manufacturing an extruded catalyst composition
US4159209A (en) * 1978-02-09 1979-06-26 Manchem Limited Metal complexes
US4462917A (en) * 1982-09-27 1984-07-31 Halliburton Company Method and compositions for fracturing subterranean formations

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